Herbicidal and plant growth-regulating substituted n-aryl nitrogen heterocycles

ABSTRACT

Intermediates of the formula ##STR1## are new, where 
     R stands for alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl, in each case having up to 20 carbon atoms, in each case optionally branched and in each case interrupted by 1 to 4 oxygen atoms, and 
     X stands for hydrogen or halogen, and are useful for synthesizing herbicidal and plant growth regulating compounds.

This is a division of application Ser. No. 354,328, filed May 19, 1989,now U.S. Pat. No. 5,039,334.

The present invention relates to novel substituted N-aryl nitrogenheterocycles, processes for their preparation and their use asherbicides and as plant growth regulators.

It is known that certain nitrogen heterocycles, such as, for example,5-tert-butyl-3-(2,4-dichloro-5-isopropoxy-phenyl)-1,3,4-oxadiazol-2-one(oxadiazone/®Ronstar) exhibit herbicidal properties (cf. U.S. Pat. No.3,835,862).

However, the action of these compounds is not satisfactory at lowapplication rates or active compound concentrations.

The novel substituted N-aryl nitrogen heterocycles of the generalformula (I) ##STR2## in which Het stands for one of the heterocyclicgroups below ##STR3## where A stands for one of the groups below##STR4## where R¹ and R² in each case independently of one another standfor hydrogen, halogen, halogenoalkyl or alkyl,

Y¹ and Y² in each case stand for oxygen or sulphur and

Z stands for hydrogen, hydroxyl or chlorine,

R stands for alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkylor cycloalkenylalkyl, in each case optionally branched and in each caseinterrupted by at least one oxygen atom, and

X stands for hydrogen or halogen,

have now been found.

Furthermore, it has been found that the novel substituted N-arylnitrogen heterocycles of the general formula (I) are obtained when

(a) in the event that Het stands for the group ##STR5## and A, R and Xhave the abovementioned meanings, cyclic anhydrides of the generalformula (II) ##STR6## in which A has the abovementioned meaning, arereacted with arylamines of the general formula (III) ##STR7## in which Rand X have the abovementioned meanings, if appropriate in the presenceof a diluent and if appropriate in the presence of a reaction auxiliary,or when

(b) in the event that Het stands for the group ##STR8## and A, R and Xhave the abovementioned meanings, substituted arylimides of the generalformula (Ia) ##STR9## in which A, R and X have the abovementionedmeanings, are reacted with a reducing agent, if appropriate in thepresence of a diluent, or when

(c) in the event that Het stands for the group ##STR10## and A, R, X andY² have the abovementioned meanings, substituted arylimides of thegeneral formula (Ia) ##STR11## in which A, R and x have theabovementioned meanings, are reacted with a sulphurizing agent, ifappropriate in the presence of a diluent, or when

(d) in the event that Het stands for the group ##STR12## and A, R and Xhave the abovementioned meanings, N-aryl nitrogen heterocycles of thegeneral formula (Ib) ##STR13## in which A, R and X have theabovementioned meanings, are reacted with thionyl chloride, ifappropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary, or when

(e) in the event that Het stands for the group ##STR14## and A, R and Xhave the abovementioned meanings, N-aryl nitrogen heterocycles of thegeneral formula (Ic) ##STR15## in which A, R and X have theabovementioned meanings, are reacted with hydrogen, in the presence of acatalyst and also if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent, or when

(f) in the event that Het stands for the group ##STR16## and A, R and Xhave the abovementioned meanings, hydroxyarylimides of the generalformula (IV) ##STR17## in which A and X have the abovementionedmeanings, are reacted with alkylating agents of the general formula (V)

    X.sup.1 --R                                                (V)

in which

R has the abovementioned meaning and

X¹ stands for a nucleophilic leaving group,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent, or when

(g) in the event that Het stands for the group ##STR18## and A and Rhave the abovementioned meanings and also

X stands for halogen, substituted arylimides of the general formula (Id)##STR19## in which A and R have the abovementioned meanings, are reactedwith a halogenating agent, if appropriate in the presence of a catalystand if appropriate in the presence of a diluent, or when

(h) in the event that Het stands for the group ##STR20## and R, R¹, R²and X have the abovementioned meanings, arylamines of the generalformula (III) ##STR21## in which R and X have the abovementionedmeanings are reacted with chloroformic acid esters of the generalformula (VI)

    R.sup.3 O--CO--CL                                          (VI)

in which R³ stands for lower alkyl, benzyl or phenyl, if appropriate inthe presence of an acid acceptor and if appropriate in the presence of adiluent, and the resulting arylurethanes of the general formula (VII)##STR22## in which R, R³ and X have the abovementioned meanings, arereacted with piperidine-2-carboxylic acid esters of the general formula(VIII) ##STR23## in which R¹ and R² have the abovementioned meanings and

R⁴ stands for lower alkyl,

if appropriate in the presence of a diluent.

Finally, it has been found that the novel substituted N-aryl nitrogenheterocycles of the general formula (I) exhibit herbicidal and plantgrowth-regulating properties.

Surprisingly, the substituted N-aryl nitrogen heterocycles of theformula (I) according to the invention have a considerably more powerfulaction against weeds than5-tert-butyl-3-(2,4-dichloro-5-isopropoxy-phenyl)-1,3,4-oxadiazol-2-one,which is a previously known active compound of similar structure and ofthe same type of action.

The invention preferably relates to compounds of the formula (I) inwhich Het stands for one of the heterocyclic groups below ##STR24##where A stands for one of the groups below ##STR25## where R¹ and R² ineach case independently of one another stand for hydrogen, fluorine,chlorine, bromine or for in each case straight-chain or branched alkylor halogenoalkyl, in each case having 1 to 3 carbon atoms and, in thecase of halogenoalkyl, having 1 to 5 identical or different halogenatoms, in particular fluorine or chlorine,

Y¹ and Y² stand for oxygen or sulphur,

Z stands for hydrogen, hydroxyl or chlorine,

R stands for alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl,or cycloalkenylalkyl, in each case having up to 20 carbon atoms, in eachcase optionally branched and in each case interrupted by 1 to 4 oxygenatoms, and

X stands for hydrogen, fluorine, chlorine or bromine.

The invention particularly relates to compounds of the formula (I) inwhich Het stands for one of the heterocyclic groups below ##STR26##where A stands for one of the groups below ##STR27## wherein R¹ and R²in each case independently of one another stand for hydrogen, methyl ortrifluoromethyl,

Y¹ and Y² stand for oxygen or sulphur,

Z stands for hydrogen, hydroxyl or chlorine,

R stands for oxaalkyl, oxaalkenyl or dioxaalkyl, in each case having upto 10 carbon atoms and in each case optionally branched, or foroxacycloalkyl-alkyl, oxacycloalkenyl-alkyl or dioxacycloalkyl-alkyl, ineach case having up to 8 carbon atoms in the oxacycloalkyl,oxacycloalkenyl or dioxacycloalkyl moiety and up to 3 carbon atoms inthe alkyl moiety, and

X stands for hydrogen, chlorine or bromine.

Examples for the compounds of the formula (I) according to the inventionare listed in Table 1 below--cf. also the Preparation Examples.

                                      TABLE 1                                     __________________________________________________________________________    Examples of the compounds of the formula (I)                                   ##STR28##                              (I)                                   Het             X R                                                           __________________________________________________________________________     ##STR29##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR30##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR31##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR32##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub. 5         ##STR33##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR34##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR35##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR36##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR37##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.3 H.sub.7          ##STR38##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9          ##STR39##      Cl                                                                               ##STR40##                                                   ##STR41##      Cl                                                                               ##STR42##                                                   ##STR43##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR44##      H CH.sub. 2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5         ##STR45##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR46##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9          ##STR47##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR48##      Cl                                                                               ##STR49##                                                   ##STR50##      Cl                                                                               ##STR51##                                                   ##STR52##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR53##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR54##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR55##      F CH.sub. 2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.3 H.sub.7         ##STR56##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9          ##STR57##      Cl                                                                               ##STR58##                                                   ##STR59##      Cl                                                                               ##STR60##                                                   ##STR61##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR62##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR63##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR64##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR65##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR66##      Cl                                                                               ##STR67##                                                   ##STR68##      Cl                                                                               ##STR69##                                                   ##STR70##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR71##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR72##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR73##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR74##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9          ##STR75##      Cl                                                                               ##STR76##                                                   ##STR77##      Cl                                                                               ##STR78##                                                   ##STR79##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR80##      H CH.sub. 2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5         ##STR81##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR82##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR83##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR84##      Cl                                                                               ##STR85##                                                   ##STR86##      Cl                                                                               ##STR87##                                                   ##STR88##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR89##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR90##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR91##      Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR92##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR93##      Cl                                                                               ##STR94##                                                   ##STR95##      Cl                                                                               ##STR96##                                                   ##STR97##      F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR98##      H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR99##      Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR100##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR101##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR102##     Cl                                                                               ##STR103##                                                  ##STR104##     Cl                                                                               ##STR105##                                                  ##STR106##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR107##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR108##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR109##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR110##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR111##     Cl                                                                               ##STR112##                                                  ##STR113##     Cl                                                                               ##STR114##                                                  ##STR115##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR116##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR117##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR118##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR119##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR120##     Cl                                                                               ##STR121##                                                  ##STR122##     Cl                                                                               ##STR123##                                                  ##STR124##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR125##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR126##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR127##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR128##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR129##     Cl                                                                               ##STR130##                                                  ##STR131##     Cl                                                                               ##STR132##                                                  ##STR133##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR134##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR135##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR136##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR137##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR138##     Cl                                                                               ##STR139##                                                  ##STR140##     Cl                                                                               ##STR141##                                                  ##STR142##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR143##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR144##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR145##     Cl                                                                              CH.sub.2 CH.sub. 2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5         ##STR146##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR147##     Cl                                                                               ##STR148##                                                  ##STR149##     Cl                                                                               ##STR150##                                                  ##STR151##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR152##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR153##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR154##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR155##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR156##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR157##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR158##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR159##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR160##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR161##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR162##     Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5          ##STR163##     Br                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                 ##STR164##     Cl                                                                               ##STR165##                                                  ##STR166##     F CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5         ##STR167##     H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9          ##STR168##

If, for example, 3,4,5,6-tetrahydrophthalic anhydride and2,4-difluoro-5-(2-(2-methoxy-ethoxy)-ethoxy)-aniline are used asstarting substances, the course of the reaction in process (a) accordingto the invention can be represented by the following equation:##STR169##

If, for example,N-(4-bromo-2-fluoro-5-(2-(2-ethoxy-ethoxy)-ethoxy)-phenyl)-dimethyl-maleimideand sodium borohydride are used as starting substances, the course ofthe reaction in process (b) according to the invention can berepresented by the following equation: ##STR170##

If, for example,N-(4-chloro-2-fluoro-5-(2,2-bis-methoxymethyl-propyl)-phenyl)-3,4,5,6-tetrahydrophthalimideand phosphorus(V) sulphide are used as starting substances, the courseof the reaction in process (c) according to the invention can berepresented by the following equation: ##STR171##

If, for example,N-(4-chloro-2-fluoro-(5-(2-(2-propoxy-ethoxy:-ethoxy)-phenyl)-3,4-dimethyl-Δ³-pyrrolin-5-ol-2-one and thionyl chloride are used as startingsubstances, the course of the reaction in process (d) according to theinvention may be represented by the following equation: ##STR172##

If, for example,N-(2,4-difluoro-5-(2-(2-butoxy-ethoxy)-ethoxy)-phenyl)-5-chloro-3,4-dimethyl-Δ³-pyrrolin-2-one is used as starting compound, the course of the reactionin process (e) according to the invention can be represented by thefollowing equation: ##STR173##

If, for example,N-(2-fluoro-5-hydroxy-phenyl)-3,4,5,6-tetrahydro-phthalimide and2-(2-methoxy-ethoxy)-ethyl methanesulphonate are used as startingsubstances, the course of the reaction in process (f) according to theinvention can be represented by the following equation: ##STR174##

If, for example,N-(2-fluoro-5-(2-(2-ethoxy-ethoxy)-ethoxy)-phenyl)-phthalimide andchlorine are used as starting substances, the course of the reaction inprocess (g) according to the invention can be represented by thefollowing equation: ##STR175##

If, for example, methyl chloroformate,4-chloro-2-fluoro-5-(2-(2-methoxy-ethoxy)-ethoxy)-aniline and ethylpiperidine-2-carboxylate are used as starting substances, the course ofthe reaction in process (h) according to the invention can berepresented by the following equation: ##STR176##

Formula (II) provides a general definition of the cyclic anhydrides tobe used as starting substances in process (a) according to theinvention, for the preparation of compounds of the formula (I).

In formula (II), A preferably, or in particular, has the meaning whichhas already been mentioned above in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, or particularly preferred, for A.

Examples of the starting substances of the formula (II) which may bementioned are: phthalic anhydride, 3,4,5,6-tetrahydro-phthalicanhydride, 3-methyl-, 4-methyl-, 4-trifluoromethyl- and3,3-dimethyl-3,4,5,6-tetrahydro-phthalic anhydride, 1,2,3,4-tetrahydro-,1,2,3,6-tetrahydro-and 2,3,4,5-tetrahydro-phthalic anhydride,3,6-dihydro-phthalic anhydride and dimethylmaleic anhydride.

The starting substances of the formula (II) are known chemicals fororganic synthesis.

Formula (III) provides a general definition of the arylamines also to beused as starting substances in process (a) according to the invention,for the preparation of compounds of the formula (I).

In formula (III), R and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R and X.

Examples of the starting substances of the formula (III) which may bementioned are: 5-(2-(2-methoxy-ethoxy)-ethoxy)-,5-(2-(2-ethoxy-ethoxy)-ethoxy)-, 5-(2-(2-propoxy-ethoxy)-ethoxy)-,5-(2-(2-isopropoxy-ethoxy)-ethoxy)-, 5-(2-(2-butoxy-ethoxy)-ethoxy)-,5-(2-(2-isobutoxy-ethoxy)-ethoxy)-, 5-(2-(2-sec-butoxy-ethoxy)-ethoxy)-,5-(2-(2-tert-butoxy-ethoxy)-ethoxy)-, 5-(2,2-bis-methoxymethyl-propoxy)-and 5-((2,2-dimethyl-1,3-dioxolan-4-yl)-methoxy)-2-fluoro-aniline,-2,4-difluoro-aniline, -4-chloro-2-fluoro-aniline and-4-bromo-2-fluoro-aniline.

The starting substances of the formula (III) were hitherto unknown fromthe literature.

The compounds of the general formula (III) are obtained when

(α) hydroxyarylamines of the general formula (IX) ##STR177## in which Xhas the abovementioned meaning, are reacted with alkylating agents ofthe general formula (V)

    X.sup.1 --R                                                (V)

in which R and X¹ have the abovementioned meanings, in the presence of adiluent, such as, for example, acetone, acetonitrile, dimethylformamide,dimethyl sulphoxide or N-methyl-pyrrolidone, if appropriate in thepresence of an acid acceptor, such as, for example, sodium carbonate,potassium carbonate, sodium hydride, potassium hydride, sodium hydroxideor potassium hydroxide, and if appropriate additionally in the presenceof water, at temperatures between 0° C. and 100° C., or when

(β) nitrophenol derivatives of the general formula (X) ##STR178## inwhich X has the abovementioned meaning, are reacted with alkylatingagents of the general formula (V)

    X.sup.1 --R                                                (V)

in which R and X¹ have the abovementioned meanings, by the techniquementioned above under (α), and the resulting compounds of the generalformula (XI) ##STR179## in which R and X have the abovementionedmeanings, are reduced by customary methods, for example using hydrogenin the presence of a catalyst, such as, for example, platinum on activecharcoal, in the presence of a diluent, such as, for example, ethanol,at temperatures between 0° C. and 100° C., or when

(γ) fluorophenol derivatives of the general formula (XII) ##STR180## inwhich X has the abovementioned meaning, are reacted with alkylatingagents of the general formula (V)

    X.sup.1 --R                                                (V)

in which R and X¹ have the abovementioned meanings, by the method giveabove under (α), and the resulting compounds of the formula (XIII)##STR181## in which R and X have the abovementioned meanings, arenitrated using nitric acid to give the compounds of the formula (XI),and the batch is then reduced by customary methods (see (β)).

The nitration can be carried out in inorganic acids, such as sulphuricacid or nitric acid, but also in organic solvents, preferably halogenohydrocarbons, such as methylene chloride, with or without the additionof salts of nitrous acid, with or without the addition of urea oramidosulphonic acid, at temperatures from -30° C. to +60° C., preferably-10° C. to +30° C.

The hydroxylarylamines of the formula (IX), the nitrophenol derivativesof the formula (X) and the phenols of the formula (XII), which are knownas starting substances, have already been disclosed (cf. EP-A 61,741).Examples of these compounds which may be mentioned are:2-chloro-4-fluorophenol and 4-fluorophenol, 2-fluoro-3-hydroxy-anilineand -nitrobenzene, 4-chloro-2-fluoro-3-hydroxy-aniline and -nitrobenzeneand also 4-bromo-2-fluoro-3-hydroxy-aniline and -nitrobenzene.

Formula (V) provides a general definition of the alkylating agents alsorequired as starting substances.

In formula (V), R preferably, or in particular, has the meaning whichhas already been mentioned above in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, or particularly preferred, for R, and X¹ preferably standsfor methylsulphonyl, phenylsulphonyl or tolylsulphonyl.

Examples of the starting substances of the formula (V) which may bementioned are: the 2-(2-methoxy-ethoxy)-ethyl ester, the2-(2-ethoxy-ethoxy)-ethyl ester, the 2-(2-propoxy-ethoxy)-ethyl ester,the 2-(2-butoxy-ethoxy)-ethyl ester, the 2-(2-isopropoxy-ethoxy)-ethylester, the 2-(2-isobutoxy-ethoxy)-ethyl ester, the2-(2-sec-butoxy-ethoxy)-ethyl ester, the 2-(2-tert-butoxy-ethoxy)-ethylester, the 2,2-bis-methoxymethyl-propyl ester and(2,2-dimethyl-1,3-dioxolan-4-yl)-methyl ester of methanesulphonic acid,benzenesulphonic acid and p-toluenesulphonic acid.

The alkylating agents of the formula (V) are known and/or can beprepared by processes known per se, for example by reacting suitablesulphonyl chlorides, such as, for example, methanesulphonyl chloride,with suitable hydroxy compounds (HOR).

Formula (Ia) provides a general definition of the substituted arylimidesto be used as starting substances in processes (b) and (c) according tothe invention, for the preparation of compounds of the formula (I).

In formula (Ia), A, R and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for A, R and X.

Examples of the starting substances of the formula (Ia) can be seen inTable 1 (above).

The substituted arylimides of the formula (Ia) are novel compoundsaccording to the invention; they can be prepared by process (a)according to the invention.

Formula (Ib) provides a general definition of the N-aryl nitrogenheterocyles to be used as starting substances in process (d) accordingto the invention, for the preparation of compounds of the formula (I).

In formula (Ib), A, R and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for A, R and X.

Examples of the starting substances of the formula (Ib) can be seen inTable 1 (above).

The N-aryl nitrogen heterocycles of the formula (Ib) are novel compoundsaccording to the invention; they can be prepared by process (b)according to the invention.

Formula (Ic) provides a general definition of the N-aryl nitrogenheterocycles to be used as starting substances in process (e) accordingto the invention, for the preparation of compounds of the formula (I).

In formula (Ic), A, R and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for A, R and X.

Examples of the starting substances of the formula (Ic) can be seen inTable 1 (above).

The N-aryl nitrogen heterocycles of the formula (Ic) are novel compoundsaccording to the invention; they can be prepared by process (d)according to the invention.

Formula (IV) provides a general definition of the hydroxyarylimides tobe used as starting substances in process (f) according to theinvention, for the preparation of compounds of the formula (I).

In formula (IV), A and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for A and X.

Examples of the starting substances of the formula (IV) which may bementioned are: N-(2-fluoro-5-hydroxy-phenyl)-,N-(2,4-difluoro-5-hydroxy-phenyl)-,N-(4-chloro-2-fluoro-5-hydroxy-phenyl)-phthalimide,N-(2-fluoro-5-hydroxy-phenyl)-, N-(2,4-difluoro-5-hydroxy-phenyl)-,N-(4-chloro-2-fluoro-5-hydroxy-phenyl)-andN-(4-bromo-2-fluoro-5-hydroxy-phenyl)-3,4,5,6-tetrahydrophthalimide,N-(2-fluoro-5-hydroxy-phenyl)-, N-(2,4-difluoro-5-hydroxy-phenyl)-,N-(4-chloro-2-fluoro-5-hydroxy-phenyl)-andN-(2-fluoro-4-bromo-5-hydroxy-phenyl)-, -3-methyl-, -4-methyl-,-4-trifluoromethyl- and -3,3-dimethyl-3,4,5,6-tetrahydrophthalimide,N-(2-fluoro-5-hydroxy-phenyl)-, N-(2,4-difluoro-5-hydroxy-phenyl)-,N-(4-chloro-2-fluoro-3-hydroxy-phenyl)-andN-(4-bromo-2-fluoro-5-hydroxy-phenyl)-3,6-dihydro-phthalimide, and alsoN-(2-fluoro-5-hydroxy-phenyl)-, N-(2,4-difluoro-5-hydroxy-phenyl-,N-(4-chloro-2-fluoro-5-hydroxy-phenyl)- andN-(4-bromo-2-fluoro-5-hydroxy-phenyl)-dimethylmaleimide.

The starting substances of the formula (IV) are known and/or can beprepared by processes known per se (cf. EP-A 61,741).

Formula (V) provides a general definition of the alkylating agents alsoto be used as starting substances in process (f) according to theinvention, for the preparation of compounds of the formula (I).

In formula (V), R preferably, or in particular, has the meaning whichhas already been mentioned above in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, or particularly preferred, for R, and X¹ preferably standsfor methylsulphonyl, phenylsulphonyl or tolylsulphonyl.

Examples of the starting substances of the formula (V) have already beenmentioned above in connection with the description of the startingsubstances in process (a) according to the invention.

Formula (Id) provides a general definition of the substituted arylimidesto be used as starting substances in process (g) according to theinvention, for the preparation of compounds of the formula (I).

In formula (Id), A and R preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for A and R.

Examples of the starting substances of the formula (Id) can be seen inTable 1 (above).

The substituted arylimides of the formula (Id) are novel compoundsaccording to the invention, they can be prepared by process (a)according to the invention.

Formula (III) provides a general definition of the arylamines to be usedas starting substances in process (h) according to the invention, forthe preparation of compounds of the formula (I).

In formula (III), R and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R and X.

Examples of the starting substances of the formula (III) and processesfor their preparation were already mentioned above in connection withthe description of the starting substances in process (a) according tothe invention.

Formula (VI) provides a general definition of the chloroformic acidesters also to be used as starting substances in process (h) accordingto the invention. In formula (VI), R³ preferably stands for methyl,benzyl or phenyl.

Examples of the starting substances of the formula (VI) which may bementioned are: methyl chloroformate, benzyl chloroformate and phenylchloroformate.

The chloroformic acid esters of the formula (VI) are known chemicals fororganic synthesis.

Formula (VIII) provides a general definition of thepiperidine-2-carboxylic acid esters also to be used as startingsubstances in process (h) according to the invention.

In formula (VIII), R¹ and R² preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R¹ and R²,and R⁴ preferably stands for methyl or ethyl.

Examples of the starting substances of the formula (VIII) which may bementioned are: methyl piperidine-2-carboxylate and ethylpiperidine-2-carboxylate.

The starting substances of the formula (VIII) are known chemicals fororganic synthesis.

Process (a) according to the invention, for the preparation of novelcompounds of the formula (I), is preferably carried out using diluents.Suitable diluents in this process are virtually all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether anddibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethylketone, methyl isopropyl ketone and methyl isobutyl ketone, carboxylicacids, such as formic acid, acetic acid or propionic acid, esters, suchas methyl acetate and ethyl acetate, nitriles, such as, for example,acetonitrile or propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide.

If appropriate, process (a) according to the invention can be carriedout in the presence of a suitable reaction auxiliary. Inorganic ororganic acids, such as, for example, acetic acid or p-toluenesulphonicacid, anhydrides, such as, for example, acetic anhydride, or acidchlorides, such as acetyl chloride, are preferably used as reactionauxiliaries. It is also possible to use other customarywater-eliminating agents, such as, for example,N,N'-dicyclohexylcarbodiimide, or customary acylating catalysts, suchas, for example, 4-(N,N-dimethylamino)-pyridine, as reactionauxiliaries.

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 20° C. and 180° C.,preferably at temperatures between 50° C. and 150° C.

For carrying out process (a) according to the invention, 1.0 to 1.5moles, preferably 1.0 to 1.2 moles, of amine of the formula (III) and ifappropriate 0.01 to 1.2 moles, preferably 0.1 to 1.0 mole, of reactionauxiliary are generally employed per mole of anhydride of the formula(II). The reaction is carried out and the reaction products are workedup and isolated by generally customary methods (cf. also the PreparationExamples).

Suitable reducing agents for carrying out process (b) according to theinvention are all reducing agents which can customarily be used forreduction reactions of this type. Complex hydrides, such as, forexample, sodium borohydride, sodium cyanoborohydride, lithiumborohydride or lithium aluminum hydride are preferably used.

Suitable diluents for carrying out process (b) according to theinvention are all customary organic or inorganic solvents, depending onthe reducing agent used. Ethers, such as diethyl ether, dioxane ortetrahydrofuran, or alcohols, such as methanol, ethanol or propanol, arepreferably used.

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a relatively wide range, depending onthe reducing agents used. In general, the process is carried out attemperatures between -20° C. and +150° C., preferably at temperaturesbetween 0° C. and 120° C.

For carrying out process (b) according to the invention, 0.1 to 2.0moles, preferably 0.25 to 1.5 moles, of reducing agent are generallyemployed per mole of substituted arylimide of the formula (Ia). Thereaction is carried out and the reaction products are worked up andisolated by generally customary methods (cf. also the PreparationExamples).

Suitable sulphurizing agents for carrying out process (c) according tothe invention are all sulphurizing agents which can customarily beemployed for sulphurizing reactions of this type. Phosphorus-sulphurcompounds, such as, for example, phosphorus(V) sulphide (P₄ S₁₀) or theso-called Lawesson reagent(2,4-bis-(4-methoxy-phenyl)-1,3-dithia-phosphetane 2,4-disulphide, arepreferably used.

Suitable diluents for carrying out process (c) according to theinvention are inert organic solvents. These preferably includealiphatic, alicyclic or aromatic, optionally halogenated hydrocarbons,such as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform andcarbon tetrachloride, and ethers, such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether.

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 180° C.,preferably at temperatures between 20° C. and 150° C.

For carrying out process (c) according to the invention, between 0.2 to2.0 moles, preferably between 0.5 and 1.5 moles, of sulphurizing agentare generally employed per mole of arylimide of the formula (Ia).

The reaction is carried out and the reaction products are worked up andisolated by a procedure known per se (cf. Bull. Soc. Chim. Belg. 87(1978), 223-228). In general, mixtures of monosulphurized anddisulphurized products are obtained in this process, which can beseparated by customary preparation methods (for example chromatographyor crystallization).

Suitable diluents for carrying out process (d) according to theinvention are inert organic solvents. These preferably includealiphatic, alicyclic or aromatic, optionally halogenated hydrocarbons,such as, for example benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform andcarbon tetrachloride, ethers, such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether, or nitriles, such as acetonitrile or propionitrile.

If appropriate, process (d) according to the invention can be carriedout in the presence of a suitable reaction auxiliary. Suitable reactionauxiliaries are, in particular, organic amines or amides. Pyridine,dimethylaniline or dimethylformamide are preferably used.

When carrying out process (d) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 120° C.,preferably at temperatures between 20° C. and 80° C.

For carrying out process (d) according to the invention, 1.0 to 5.0moles, preferably 1.0 to 2.0 moles, of thionyl chloride and ifappropriate 0.1 to 2.0 moles, preferably 0.5 to 1.5 moles, of reactionauxiliary are generally employed per mole of N-aryl nitrogen heterocycleof the formula (Ib).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods.

Suitable catalysts for carrying out process (e) according to theinvention are all customary hydrogenation catalysts. Noble metalcatalysts, such as, for example, platinum, platinum oxide, palladium orruthenium, if appropriate on a suitable carrier, such as, for example,carbon or silicon dioxide, are preferably used.

Suitable diluents for carrying out process (e) according to theinvention are inert organic solvents. These preferably include aliphaticor alicyclic, optionally halogenated hydrocarbons, such as, for example,benzine, petroleum ether, hexane, cyclohexane, dichloromethane,chloroform, carbon tetrachloride, ethers, such as diethyl ether,dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethyleneglycol diethyl ether, or alcohols, such as methanol, ethanol orpropanol.

If appropriate, process (e) according to the invention can be carriedout in the presence of a suitable acid-binding agent. Alkali metalcarbonates, such as sodium carbonate or potassium carbonate, or organicbases, such as pyridine or lutidine, are preferably used.

When carrying out process (e) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between -20° C. and 100° C.,preferably at temperatures between 0° C. and 50° C.

The process according to the invention can be carried out underatmospheric pressure or under increased pressure. The process ispreferably carried out under atmospheric pressure.

For carrying out process (e) according to the invention, 1.0 to 3.0moles, preferably 1.0 to 1.5 moles, of hydrogen and if appropriate 1.0to 3.0 moles, preferably 1.0 to 1.5 moles, of acid-binding agent aregenerally employed per mole of N-aryl nitrogen heterocycle of theformula (Ic). The reaction is carried out and the reaction products areworked up and isolated by generally customary methods.

Process (f) according to the invention, for the preparation of the novelcompounds of the formula (I), is preferably carried out using diluents.Suitable diluents for this process are virtually all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether anddibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethylketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, suchas methyl acetate and ethyl acetate, nitriles, such as, for example,acetonitrile and propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide.

Acid acceptors which can be employed in process (f) according to theinvention are all acid-binding agents which can customarily be employedfor reactions of this type. Alkali metal hydroxides, such as, forexample, sodium hydroxide and potassium hydroxide, alkaline earth metalhydroxides, such as, for example, calcium hydroxide, alkali metalcarbonates and alkali metal alkoxides, such as sodium carbonate,potassium carbonate, sodium tert-butoxide and potassium tert-butoxide,furthermore aliphatic, aromatic or heterocyclic amines, for exampletriethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine,pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2,2,2]-octane (DABCO), are preferably suitable.

In process (f) according to the invention, the reaction temperatures canbe varied within a relatively wide range. In general, the process iscarried out at temperatures between 0° C. and 150° C., preferably attemperatures between 10° C. and 100° C.

Process (f) according to the invention is generally carried out underatmospheric pressure.

For carrying out process (f) according to the invention, between 1 and 2moles, preferably between 1.1 and 1.5 moles, of alkylating agent of theformula (V) is generally employed per mole of hydroxyarylimide of theformula (IV).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods.

Suitable halogenating agents for carrying out process (g) according tothe invention are the customary halogenating agents which can be usedfor halogenating aromatic compounds. Elemental halogens, such aschlorine or bromine, or halogen compounds, such as sulphuryl chloride,are preferably used.

If appropriate, process (g) is carried out using catalysts. Suitablecatalysts are preferably acid or electrophilic halogen compounds, suchas, for example, hydrogen chloride, hydrogen bromide, aluminum chloride,aluminum bromide, iron(III) chloride or iron(III) bromide.

Process (g) according to the invention is preferably carried out usingdiluents. Suitable diluents are above all those organic solvents whichhave already been mentioned above in process (f), but also acetic acidand/or water.

In process (g) according to the invention, the reaction temperatures canbe varied within a relatively wide range. In general, the process iscarried out at temperatures between 0° C. and 150° C., preferably attemperatures between 20° C. and 120° C.

Process (g) is generally carried out under atmospheric pressure.

For carrying out process (g) according to the invention, between 1 and 5moles, preferably between 1 and 3 moles, of halogenating agent aregenerally employed per mole of starting compound of the formula (Id).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods.

Process (h) according to the invention is preferably carried out usingdiluents. Suitable diluents are above all those organic solvents whichhave already been mentioned above in process (f), and additionally, inthe second step, preferably also alcohols, such as methanol, ethanol orisopropanol.

Process (h) according to the invention is preferably carried out in thepresence of an acid acceptor. Suitable acid acceptors are above allthose acid-binding agents which have already been mentioned above inprocess (f).

In process (h) according to the invention, the reaction temperatures canbe varied within a relatively wide range. In general, the process iscarried out at temperatures between -20° C. and +150° C., preferably attemperatures between 0° C. and 100° C.

Process (h) according to the invention is generally carried out underatmospheric pressure.

For carrying out process (h) according to the invention, between 0.8 and1.5 moles, preferably between 1.0 and 1.2 moles, of chloroformic acidester of the formula (VI) are generally employed per mole of arylamineof the formula (III), and between 0.8 and 1.5 moles, preferably between1.0 and 1.2 moles, of piperidine-2-carboxylic acid of the formula (VIII)are generally employed per mole of arylurethane of the formula (VII).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

The compounds of the formula (I) according to the invention areparticularly suitable for selectively combating dicotyledon weeds usingthe pre-emergence method and the post-emergence method.

The active compounds according to the invention engage in the metabolismof the plants and can therefore be employed as growth regulators.

Experience to date of the mode of action of plant growth regulators hasshown that an active compound can also exert several different actionson plants. The actions of the compounds depend essentially on the pointin time at which they are used, relative to the stage of development ofthe plant, and on the amounts of active compound applied to the plantsor their environment and the way in which the compounds are applied. Inevery case, growth regulators are intended to influence the crop plantsin the particular manner desired.

The amount of leaves on plants can be controlled, under the influence ofgrowth regulators, so that defoliation of the plants at a desired pointin time is achieved. Such defoliation is of great importance in themechanical harvesting of cotton, but is also of interest forfacilitating harvesting in other crops, such as, for example, inviticulture. Defoliation of the plants can also be carried out to lowerthe transpiration of plants before they are transplanted.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,pastes, soluble powders, granules, suspension-emulsion concentrates,natural and synthetic substances impregnated with active compound andvery fine capsules in polymeric substances and in coating compositionsfor seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, and/orsolid carriers, optionally with the use of surface-active agents, thatis, emulsifying agents and/or dispersing agents, and/or foam-formingagents. In the case of the use of water as an extender, organic solventscan, for example, also be used as auxiliary solvents. As liquidsolvents, there are suitable in the main aromatics, such as xylene,toluene or alkylnaphthalenes, chlorinated aromatics or chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetable oil,alcohols, such as butanol or glycol as well as their ethers and esters,ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

As solid carriers there are suitable, for example, ammonium salts,ground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable, for example, crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable, for example, non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable,for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic polymersin the form of powders, granules or latices, such as gum arabic,polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin the form of their formulations and can also be used as mixtures withknown herbicides for combating weeds, finished formulations or tankmixes being possible.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethylurea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets, and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans. 2,4-dichlorophenoxyaceticacid (2,4-D); 4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB);2,4-dichlorophenoxy propionic acid (2,4-DP); methyl2-[[[[[4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-methyl]-benzoate(BENSULFURON), 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide(BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxybenzonitrile (BROMOXYNIL);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLORTOLURON); 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, itsmethyl ester or its ethyl ester (DICLOFOP);4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN);2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methylester or its ethyl ester (FENOXAPROP); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ); 3,5-diido-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)-propionic acid (MCPP);N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET);2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoicacid or its methyl ester (METSULFURON); S-ethylN,N-hexamethylenethiocarbamate (MOLINATE)4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide (ORYZALIN)N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro-aniline (PENDIMETHALIN);O-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE);2,4-bis-[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMETRYNE)4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate(THIAMETURON), S-(2,3,3-trichloroallyl N,N-diisopropylthiocarbamate(TRIALLATE) and 3,5,6-trichloro-2-pyridyloxyacetic acid (TRICLOPYR).Surprisingly, some mixtures also show synergistic action.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 15 kg of active compound perhectare of soil surface, preferably between 0.05 and 10 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR182##

Process (a)

A mixture of 6.4 g (0.023 mol) of4-chloro-2-fluoro-5-(2-(2-ethoxy-ethoxy)-ethoxy)-aniline, 3.7 g (0.024mol) of 3,4,5,6-tetrahydrophthalic anhydride and 60 ml of acetic acid isstirred for 5 hours at 80° C. When the reaction mixture is cold, it isdiluted with water and extracted using methylene chloride. The organicphase is washed using sodium bicarbonate solution, dried over magnesiumsulphate and concentrated in vacuo. The resulting dark oil is subjectedto purification by column chromatography on silica gel usingcyclohexane/ethyl acetate (1:1) as the eluent.

4.8 g (50.7% of theory) ofN-[4-chloro-2-fluoro-5-[2-(2-ethoxy-ethoxy)-ethoxy]-phenyl]-3,4,5,6-tetrahydrophthalimideare obtained as colorless crystals of melting point 61° C.

EXAMPLE 2 ##STR183##

Process (h)

A solution of 1.4 ml (11 mmol) of phenyl chloroformate in 15 ml ofmethylene chloride and 15 ml of 1N sodium hydroxide solution are addedsimultaneously to a stirred solution of 3.05 g (11 mmol) of4-chloro-2-fluoro-5-((2,2-dimethyl-1,3-dioxolan-4-yl)-methoxy)-anilinein 20 ml of methylene chloride, which is cooled at 0° C. to 5° C. Themixture is stirred for 30 minutes, the organic phase is then separatedoff and the aqueous phase is re-extracted using methylene chloride; theorganic phases are combined, dried using sodium sulphate and filtered.The solvent is removed from the filtrate by distillation under awaterpump vacuum, the residue is taken up in 20 ml of propanol, 1.73 g(11 mmol) of ethyl piperidine-2-carboxylate are added, and the mixtureis refluxed for 6 hours. The mixture is concentrated and the residue isthen taken up in methylene chloride, and this solution is washed with 1Nsodium hydroxide solution, dried using sodium sulphate and filtered. Thefiltrate is concentrated and the residue is purified by columnchromatography (on silica gel using cyclohexane/ethyl acetate, 2:3).

1.85 g (41% of theory) of2-(4-chloro-2-fluoro-5-((2,2-dimethyl-1,3-dioxolan-4-yl)-methoxy)-phenyl)-5,6,7,8-tetrahydroimidazo[1,5a]-pyridine-1,3(2H,8aH)-dioneare obtained as an oil.

¹ H-NMR (200 MHz, CDCl₃, δ): 1.40 and 1.46 (2s, 6H, 2x CH₃); 4.48 (m,1H, --OCH<); 6.88 (d, 1H, ##STR184## 7.29 (d, 1H, ##STR185##

The compounds of the formula (I) listed in Table 2 below can be obtainedanalogously to Example 1 or 2 and/or following the general instructionsof the preparation processes according to the invention.

                                      TABLE 2                                     __________________________________________________________________________    Examples of the compounds of the formula (I)                                   ##STR186##                                      (I)                                                                   Physical data                        Example No.                                                                          Het          X R                  (melting point                       __________________________________________________________________________                                             °C.)                                  ##STR187##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5     4                                                                                     ##STR188##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9     5                                                                                     ##STR189##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.4 H.sub.9     6                                                                                     ##STR190##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3            7                                                                                     ##STR191##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3             8                                                                                     ##STR192##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OC.sub.2 H.sub.5     9                                                                                     ##STR193##  Cl                                                                               ##STR194##        75                                   10                                                                                    ##STR195##  Cl                                                                               ##STR196##        78                                   11                                                                                    ##STR197##  Cl                                                                              CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OCH.sub.3                                                     Oil                                  __________________________________________________________________________

STARTING SUBSTANCES OF THE FORMULA (III) EXAMPLE (III-1) ##STR198##

20 g (0.124 mol) of 4-chloro-2-fluoro-5-hydroxyaniline are dissolved in140 ml of N-methylpyrrolidone, and 10.2 g (0.186 mol) of potassiumhydroxide in 12 ml of water and also 35.6 g (0.130 mol) of2-(2-methoxy-ethoxy)-ethyl p-toluenesulphonate are added in succession.The mixture is stirred at room temperature for 18 hours, and most of thesolvent is then removed in vacuo. 200 ml of water are added to the oilyresidue, and the oil which separates is extracted using dichloromethane.The organic phase is separated off, washed, dried and concentrated invacuo.

As the residue, 30.5 g (93.3% of theory) of4-chloro-2-fluoro-5-[2-(2-methoxy-ethoxy)-ethoxy]-aniline remain as anoil.

¹ H-NMR (CDCl₃): δ=6.98 ppm (1H, d).

EXAMPLE (III-2) ##STR199##

5.5 g (0.018 mol) of2-chloro-4-fluoro-5-nitro-[2-(2-ethoxy-ethoxy)-ethyl]-phenol aredissolved in 100 ml of ethanol, 1.0 g of 5% platinum on active charcoalare added, and the mixture is hydrogenated at 40° C. using hydrogenunder atmospheric pressure. When the reaction is complete, the catalystis filtered off and the solvent is removed in vacuo.

4.5 g (90.7% of theory) of4-chloro-2-fluoro-5-[2-(2-ethoxy-ethoxy)-ethoxy]-aniline are obtained asan oil.

¹ H-NMR (CDCl₃): δ=7.00 ppm (1H, d).

STARTING SUBSTANCES OF THE FORMULA (XI) EXAMPLE (XI-1) ##STR200##

5 g (0.026 mol) of 2-chloro-4-fluoro-5-nitrophenol are dissolved in 10ml of dimethyl sulphoxide and 0.8 g (0.0267 mol) of sodium hydride (80%strength) and 7.7 g (0.0267 mol) of 2-(2-ethoxy-ethoxy)-ethylp-toluenesulphonate are added in succession. The mixture is heated at80° C. for 8 hours, then poured out into water, and the precipitated oilis extracted using dichloromethane. The organic phase is washed, driedand concentrated.

5.9 g (72% of theory) of4-chloro-2-fluoro-5-[2-(2-ethoxy-ethoxy)-ethoxy]-nitrobenzene areobtained.

¹ H-NMR (CDCl₃): δ=7.70 ppm (1H, d).

USE EXAMPLES

In the following Use Examples, the compound listed below is used ascomparison substance: ##STR201##5-tert-butyl-3-(2,4-dichloro-5-isopropoxy-phenyl)-1,3,4-oxadiazol-2-one(oxadiazone/®Ronstar)--disclosed in U.S. Pat. No. 3,835,862.

EXAMPLE A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example the compound of Preparation Example (1) has aclearly superior activity compared with the known compound (A).

EXAMPLE B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example the compound of Preparation Example (1) has aclearly superior activity compared with the known compound (A).

EXAMPLE C Defoliation and Desiccation of the Leaves of Cotton

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier and the mixture is made up to the desired concentration withwater.

Cotton plants are grown in a greenhouse until the 5th secondary leaf hasunfolded completely. In this stage, the plants are sprayed with thepreparations of active compound until dripping wet. After 1 week, theshedding of leaves and the desiccation of the leaves are rated, incomparison with the control plants.

In this test, for example, the compound of Preparation Example (1) showsa clear superiority compared with the untreated control.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. An arylamine of the formula ##STR202## in which R standsfor alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl orcycloalkenylalkyl, in each case having up to 20 carbon atoms, each ofwhich is optionally branched and each of which is interrupted by 1 to 4oxygen atoms, andX stands for hydrogen or halogen.
 2. An arylamineaccording to claim 1, in whichR stands for oxaalkyl, oxaalkenyl ordioxaalkyl, in each case having up to 10 carbon atoms and in each caseoptionally branched, or for oxacycloalkyl-alkyl, oxacycloalkenylalkyl,or dioxacycloalkyl-alkyl, in each case having up to 8 carbon atoms inthe oxacycloalkyl, oxacycloalkenyl or dioxacycloalkyl moiety and up to 3carbon atoms in the alkyl moiety.
 3. An arylamine according to claim 1,wherein such compound is4-chloro-2-fluoro-5-[2-(2-ethoxy-ethoxy)-ethoxy]-aniline of the formula##STR203##